Synthesis Of Primary Alcohols Research Articles

Hydrogenation of Epoxides to Anti‐Markovnikov Alcohols over a Nickel Heterogenous Catalyst Prepared from Biomass (Rice) Waste

AbstractThe synthesis of primary alcohols (from olefins) is an important and challenging transformation, as most of the current methods suffer from regioselectivity issues. This work describes the utilization of rice husk (RH) from agricultural waste as support for the preparation of a catalyst for the conversion of olefin oxides to primary alcohols. The catalyst was synthesized by pyrolysis of RH impregnated with nickel, and characterized by IR, AAS, XRD, BET, XPS, TEM, and TPD technics. The catalyst shows excellent activity and selectivity towards anti‐Markovnikov alcohols, acting simultaneously as Brønsted acid, solid Lewis acid, and as hydrogenation catalyst. A substrate screening was done, the catalyst's recycling stability was assessed, and a plausibly reaction mechanism was proposed.

Synthesis of Secondary Monoalcohols from Terminal Vicinal Alcohols over Silica-Supported Rhenium-Modified Ruthenium Catalyst

The selective synthesis of secondary alcohols from 1,2-alkanediol by C–O hydrogenolysis, which has been less investigated than the synthesis of primary alcohols, was investigated with Ru-based catalysts and 1,2-propanediol (1,2-PrD) as a model substrate. The modification of Ru/SiO2 with ReOx achieved significant improvement of activity. The hydrogenolysis of 1,2-PrD over Ru–ReOx/SiO2 (Re/Ru = 0.5) initially formed both 2-propanol (2-PrOH) and 1-propanol (1-PrOH) with similar selectivity along with the formation of ≤ C2 compounds, and then 1-PrOH was preferably converted to propane; as a result, only 2-PrOH remained in the liquid phase with 23% yield at longer reaction time. This catalyst was reusable at least twice. The characterization with H2-TPR, XRD, TEM-EDX, XANES, and EXAFS showed that the Ru species in the Ru–ReOx/SiO2 catalysts were completely reduced in the reaction conditions, while a part of Re species were also reduced to partially reduced monomeric species (Reδ+Ox) without Re–Re direct bond located on the surface of Ru metal particles. This ReOx-modified Ru metal surface probably works as the active sites. The excess Re species was reduced to large Re metal particles; however, these Re metal particles are not involved in the catalysis.

Ethylene-driven changes in epicuticular wax metabolism in citrus fruit

Epicuticular waxes are important natural compounds that influence cuticle properties and can protect fruit from factors that harm its external quality. We demonstrated that, at a dose that reduces postharvest citrus fruit quality loss (4 d 2 µL L−1), ethylene redirected epicuticular wax metabolism towards the synthesis of primary alcohols, mostly behenyl alcohol, by favouring the acyl-reduction pathway. This treatment also reduced the synthesis of terpenoids by redirecting the mevalonate pathway towards farnesol accumulation to the detriment of the accumulation of most triterpenoids, but not of their precursor squalene. Moreover, the 4 d ethylene treatment sharply increased the synthesis of docosane and lignoceric acid and lowered that of cerotic acid. Longer ethylene exposure (8 d) reversed some of these effects by lowering the contents of most alcohols, lignoceric acid and squalene, while increasing that of its derivative sitosterol. The 8 d ethylene treatment also increased farnesol and docosane contents.

FAR5, a fatty acyl-coenzyme A reductase, is involved in primary alcohol biosynthesis of the leaf blade cuticular wax in wheat (Triticum aestivum L.).

A waxy cuticle that serves as a protective barrier against non-stomatal water loss and environmental damage coats the aerial surfaces of land plants. It comprises a cutin polymer matrix and waxes. Cuticular waxes are complex mixtures of very long chain fatty acids (VLCFAs) and their derivatives. Results show that primary alcohols are the major components of bread wheat (Triticum aestivum L.) leaf blade cuticular waxes. Here, the characterization of TaFAR5 from wheat cv Xinong 2718, which is allelic to TAA1b, an anther-specific gene, is reported. Evidence is presented for a new function for TaFAR5 in the biosynthesis of primary alcohols of leaf blade cuticular wax in wheat. Expression of TaFAR5 cDNA in yeast (Saccharomyces cerevisiae) led to production of C22:0 primary alcohol. The transgenic expression of TaFAR5 in tomato (Solanum lycopersicum) cv MicroTom leaves resulted in the accumulation of C26:0, C28:0, and C30:0 primary alcohols. TaFAR5 encodes an alcohol-forming fatty acyl-coenzyme A reductase (FAR). Expression analysis revealed that TaFAR5 was expressed at high levels in the leaf blades, anthers, pistils, and seeds. Fully functional green fluorescent protein-tagged TaFAR5 protein was localized to the endoplasmic reticulum (ER), the site of primary alcohol biosynthesis. SDS-PAGE analysis indicated that the TaFAR5 protein possessed a molecular mass of 58.4kDa, and it was also shown that TaFAR5 transcript levels were regulated in response to drought, cold, and abscisic acid (ABA). Overall, these data suggest that TaFAR5 plays an important role in the synthesis of primary alcohols in wheat leaf blade.

Homogeneous Pd-catalyzed transformation of terminal alkenes into primary allylic alcohols and derivatives.

Synthesis of primary alcohols from terminal alkenes is an important process in both bulk and fine chemical syntheses. Herein, a homogeneous Pd-complex-catalyzed transformation of terminal alkenes into primary allylic alcohols, by using 5 mol % [Pd(PPh3)4] as a catalyst, and H2O, CO2, and quinone derivatives as reagents, is reported. When alcohols were used instead of H2O, allylic ethers were obtained. A proposed mechanism includes the addition of oxygen nucleophiles at the less-hindered terminal position of π-allyl Pd intermediates.

His-tagged Horse Liver Alcohol Dehydrogenase: Immobilization and application in the bio-based enantioselective synthesis of (S)-arylpropanols

The novel histidine-tagged Horse Liver Alcohol Dehydrogenase (His-HLADH-EE) was successfully purified and covalently immobilized onto a solid support in a one-step procedure through a metal-directed technique. A full characterization of the immobilized enzyme was carried out. Effects of pH, temperature and organic co-solvents were deeply investigated and they showed a shift in the optimum pH with respect to the free form as well as increased stability to temperature and solvents. The immobilized His-HLADH-EE proved to be effective as catalyst in the reduction of aliphatic and aromatic aldehydes. Application of the free and immobilized His-HLADH-EE to the chemo-enzymatic synthesis of (S)-Profenols demonstrated enhanced enantioselectivity and high reusability of the immobilized form. The achievement of a robust and effective immobilization of an alcohol dehydrogenase substantiated the use of biocatalytic reduction in the synthesis of primary alcohols and valuable chiral intermediates especially for pharmaceutical industries.

Chemoenzymatic Synthesis of Primary Alcohols with a 2-Isoxazoline Moiety

Racemic 2-isoxazoline-5-carboxylate esters were reduced under mild conditions to form the corresponding primary alcohols. These alcohols were enzymically resolved by acylation with succinic anhydride in the presence of Amano AK lipase.